Efficient combined regulator for easily-argillized copper oxide cobalt ore and beneficiation method

Abstract

The invention discloses an efficient combined regulator for easily-argillized copper oxide cobalt ore and a beneficiation method. The efficient combined regulator comprises the following components in parts by weight: 250-350 parts of sodium citrate and 1100-1200 parts of sodium hydrosulfide. Sodium citrate has high dispersing capacity, and the efficiency of selective adsorption between the argillization copper-cobalt ore and the medicament can be improved; meanwhile, the complexing ability of sodium citrate on ions, such as Fe, Ca and Mg, influencing agent adsorption on the surface of the ore is high, in addition, products obtained after complexing of the Fe, Ca and Mg ions can be dissolved in water, and action sites are provided for selective adsorption of a vulcanizing agent (NaHS) and a collecting agent amyl xanthate (PAX). According to the combined regulator and the beneficiation method provided by the invention, the problem of poor reagent selectivity in the flotation process of the argillization copper-cobalt ore can be obviously improved, the vulcanization effect of a vulcanizing agent is enhanced, and selective adsorption of a collecting agent is promoted, so that the recovery rate of copper and cobalt metals in the copper-cobalt oxide ore under the condition of serious ore argillization is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of mineral processing, and particularly relates to a high-efficiency combined regulator for easily slime-forming copper oxide cobalt ore and a beneficiation method. Background Art

[0002] Sulphide flotation is one of the important processes for treating copper oxide cobalt ore at present. The specific process is to first sulphidize the copper oxide cobalt ore with a sulphidizing agent to enhance its affinity with the collector, and then use a sulphide ore collector such as xanthate to selectively float the valuable minerals. When the sulphide flotation process is used to float copper cobalt ore that is easy to slime, there are problems such as poor separation efficiency and low recovery rates of copper and cobalt. However, with the continuous development and utilization of high-quality resources, easily slime-forming copper oxide cobalt ore has gradually become the main force in the production of copper and cobalt metals (Yue Meng Lin, Bai Sui Han, Li Shuai Jiang, etc., Research Status and Prospect of Flotation Methods and Reagents for Copper Oxide Ore, Comprehensive Utilization of Minerals, 2024, 45(3): 112-120.). Therefore, the high-efficiency recovery technology for easily slime-forming copper oxide cobalt ore needs to be further improved.

[0003] The quality of flotation indexes depends on the physical and chemical properties of the ore (Hai Jun Chen. Experimental Study on Optimization of Parameters for Sulfuric Acid Pre-oxidation-Flotation Separation of Copper-Lead Mixed Concentrate [J]. Nonferrous Metals Engineering, 2024, 15(5): 95-103.). Solution ions in the pulp are prone to chemical reactions with slime particles, causing the slime fine particles to non-selectively deposit on the ore surface, resulting in a homogenization effect between the valuable minerals and gangue minerals, affecting the non-selective adsorption of the collector, and thus deteriorating the separation between ores (Hai Ping Zhao, Jing Zhi Liu, Xue Ping Hu, etc. Application of Sodium Amino Phosphate in High-Efficiency Separation of Carlin-Type Gold Ore [J]. Nonferrous Metals Engineering, 2024, 14(6): 90-98.). In summary, the high-efficiency separation of easily slime-forming copper cobalt ore should start from the development of high-efficiency regulators, and develop more efficient regulators to improve the selective adsorption effect of sulphidizing agents and collectors on the mineral surface (Zhao Wei, Wei Sun, Qing Peng Zhang, etc. Flotation Separation of Fine-Grained Sulphide Copper Ore and Easily Slime-forming Calcium Magnesium Minerals [J]. Nonferrous Metals Engineering, 2017, 7(4): 64-69.).

[0004] In current research, the improvement of the flotation effect of easily slime-forming copper cobalt ore mostly focuses on enhancing the sulphidizing effect of the sulphidizing agent. For example, Dai Xiong Chen et al. (Dai Xiong Chen, Meng Fei Liu, Song Jiang Li, etc., Activation Sulphide Flotation Mechanism of Copper Oxide Ore and Its Industrial Application [J]. The Chinese Journal of Nonferrous Metals, 2022(8): 2393-2404.) added NH4 during the flotation process +To enhance the effect of the vulcanizing agent, but this technology has the problem that the dosage of the vulcanizing agent is difficult to control. Excessive vulcanizing agent may produce the opposite effect. More importantly, this technology has not solved the problems of large dosage of the agent and poor separation efficiency. At the same time, for ores that are prone to slime, some researchers recommend using the means of desliming (Lin Yuemeng, Han Baisui, Jiang Lishuai, etc., Research Status and Prospect of Flotation Methods and Agents for Copper Oxide Ores, Comprehensive Utilization of Minerals, 2024, 45(3): 112 - 120.). Although this process can improve the concentrate quality to a certain extent, a part of copper and cobalt metals are still contained in the removed fine particles, resulting in waste of ore resources. Therefore, developing an efficient regulator that can promote the selective adsorption of vulcanizing agents and collectors is an effective way to solve the problem of difficult flotation recovery of slime - prone ores. However, currently, the disclosed copper oxide mineral regulators on the market, such as lignosulfonate (Chinese Patent Application CN103480500A) and imidazole hydroxide + sodium sulfite (Chinese Patent Application CN117380401A), have problems of high reagent cost and poor effect when flotation of slime - prone copper - cobalt ores. In summary, the efficient regulator for slime - prone copper - cobalt ores still needs to be further optimized. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the present invention aims to provide an efficient combined regulator and a beneficiation method for slime - prone copper oxide cobalt ores.

[0006] To achieve the above - mentioned purpose, the present invention adopts the following technical solutions:

[0007] The present invention provides an efficient combined regulator for slime - prone copper oxide cobalt ores, which includes 250 - 350 parts by weight of sodium citrate and 1100 - 1200 parts by weight of sodium hydrosulfide.

[0008] The present invention also provides a beneficiation method for slime - prone copper oxide cobalt ores using the above - mentioned efficient combined regulator, which includes the following steps:

[0009] S1. Crush the raw ore and set it aside for later use;

[0010] S2. Take the crushed ore obtained in step S1, mix it with water and then grind it to obtain a flotable product;

[0011] S3. Conduct multi - stage mixed flotation of sulfide ore and oxide ore on the flotable product obtained in step S2; In the first - stage flotation process, add the regulator NaHS, collector and frother to pre - float out a part of the fine slime;

[0012] After the first-stage flotation is completed, the tailings remaining after a part of the fine slime is floated are subjected to subsequent flotation; before each subsequent stage of flotation, the high-efficiency combined regulator and collector described in claim 1 are added in advance, and after stirring and pulp conditioning, flotation is carried out to obtain concentrate and tailings. The tailings remaining from each stage of flotation enter the next stage of flotation, and the concentrates obtained from each stage of flotation are mixed to obtain the final copper oxide-cobalt concentrate. The tailings remaining after the fifth-stage flotation are the final tailings.

[0013] Further, in step S1, the raw ore is crushed to a particle size ≤ 2 mm.

[0014] Further, in step S2, the grinding is carried out using a ball mill, and the ball mill uses iron ball media with a filling rate of 32%.

[0015] Further, in the flotable product obtained in step S2, the part with a particle size ≤ 74 μm accounts for 67 - 77% of the total mass of the flotable product.

[0016] Further, in step S3, in the first-stage flotation, the pulp pH is 9 - 10, and the mass concentration of the pulp is 28 - 34%; in the first-stage flotation, the dosage of the regulator NaHS is 500 - 700 g / t of the dry weight of the raw ore, the collector used includes amyl xanthate with a dosage of 500 - 700 g / t of the dry weight of the raw ore, and the frother used includes 2 # oil with a dosage of 20 - 40 g / t of the dry weight of the raw ore.

[0017] Furthermore, in step S3, in each stage of flotation after the first-stage flotation, the collector used includes amyl xanthate.

[0018] Still further, in step S3, the total dosage of the collector amyl xanthate in all stages of flotation is 1800 - 1900 g / t of the dry weight of the raw ore.

[0019] Further, in step S3, the total dosage of the high-efficiency combined regulator in all stages of flotation is 250 - 350 g of sodium citrate and 1100 - 1200 g / t of the dry weight of the raw ore of sodium hydrosulfide.

[0020] The beneficial effects of the present invention are as follows: Mineral slime formation leads to non-selective adsorption of sulfiding agent (NaHS) and collector amyl xanthate (PAX) on the surfaces of valuable ores and gangues, resulting in problems in the flotation process of copper-cobalt oxide ores, such as high reagent costs, poor separation efficiency between valuable minerals and gangue minerals in flotation concentrates, and low flotation recovery efficiency of copper and cobalt metals. In response to this, the present invention provides a high-efficiency combination regulator of sodium citrate and sodium hydrosulfide. Sodium citrate has strong dispersing ability, which can improve the selective adsorption efficiency between slime-forming copper-cobalt ores and reagents; at the same time, sodium citrate has strong complexing ability with ions such as Fe, Ca, and Mg on the ore surface that affect the selective adsorption of reagents, and the products after complexing Fe, Ca, and Mg ions are water-soluble, providing active sites for the selective adsorption of sulfiding agent (NaHS) and collector amyl xanthate (PAX), which can significantly improve the problem of poor reagent selectivity, enhance the effect of the sulfiding agent, promote the selective adsorption of the collector, and thus improve the recovery rate of copper and cobalt metals in copper-cobalt oxide ores under severe ore slime conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a flowchart of the method of Embodiments 1-3 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0022] The present invention will be further described below with reference to the drawings. It should be noted that this embodiment is based on the present technical solution, and detailed implementation manners and specific operation processes are given, but the protection scope of the present invention is not limited to this embodiment.

[0023] Embodiment 1

[0024] This embodiment provides a beneficiation method for easily slime-forming copper-cobalt oxide ores. As Figure 1 shown, the specific process is as follows:

[0025] The raw ore is crushed by a New Zealand crusher to a particle size ≤ 2 mm, and after being mixed evenly, it is reserved for use. Take 500 g of the evenly mixed sample and mix it with 215 mL of water, then place it in a ball mill with iron ball media having a filling rate of 32%, and grind for 3.5 minutes to obtain a flotable product. The part with a particle size ≤ 74 μm in the flotable product accounts for 72% of the total mass of the product.

[0026] The obtained flotable product is subjected to five-stage all-open-circuit sulfur-oxygen mixed flotation. Considering the serious ore slime formation, no combination regulator is added in the first-stage flotation process, but 600 g / t of the original ore dry weight of the regulator sodium hydrosulfide (stir for 2 minutes), 600 g / t of the original ore dry weight of the collector amyl xanthate (stir for 2 minutes) and 2 #30 g / t of the original ore dry weight of oil (stir for 1 minute) is used to pre-flotate a part of the slime first (the first-stage flotation time is 5 minutes), so as to weaken the influence of the slime on the subsequent flotation, and at the same time, the dosage of the high-efficiency combined regulator can be reduced to lower the reagent cost. In the first-stage flotation, the pulp pH is maintained in an alkaline environment of 9.5, and the pulp mass concentration is about 30%.

[0027] Before the second-stage and third-stage flotation, a high-efficiency combined regulator (100 g / t of the original ore dry weight of sodium citrate + 400 g / t of the original ore dry weight of sodium hydrosulfide) is added first and stirred for 2 minutes for pulp conditioning. Then, 400 g / t of the original ore dry weight of the collector amyl xanthate (PAX) is added and stirred for 2 minutes, and finally the flotation starts. The flotation time for both the second-stage and third-stage is 5 minutes; before the fourth-stage flotation, a high-efficiency combined collector (50 g / t of the original ore dry weight of sodium citrate + 300 g / t of the original ore dry weight of sodium hydrosulfide) is added and stirred for 2 minutes for pulp conditioning. Then, 300 g / t of the original ore dry weight of the collector amyl xanthate (PAX) is added and stirred for 2 minutes, and the flotation time is 4 minutes; before the fifth-stage flotation, a high-efficiency combined collector (50 g / t of the original ore dry weight of sodium citrate + 50 g / t of the original ore dry weight of sodium hydrosulfide) is added and stirred for 2 minutes for pulp conditioning. Then, 200 g / t of the original ore dry weight of the collector amyl xanthate (PAX) is added and stirred for 2 minutes, and the flotation time is 3 minutes. The tailings remaining from each stage of flotation enter the next stage of flotation. The concentrates obtained from each stage of flotation are mixed to obtain the final copper-cobalt oxide concentrate, and the tailings remaining after the fifth-stage flotation are the final tailings.

[0028] In this embodiment, during the entire flotation process, the total dosage of the high-efficiency combined regulator is 1450 g / t of the original ore dry weight, which includes 300 g / t of the original ore dry weight of sodium citrate and 1150 g / t of the original ore dry weight of sodium hydrosulfide. The total dosage of the collector amyl xanthate (PAX) is 1900 g / t of the original ore dry weight.

[0029] In the above method, in a flotation environment with serious slime of the ore, a part of the slime is first flotated using the conventional regulator sodium hydrosulfide, collector, and frother. Starting from the second-stage flotation, a high-efficiency combined regulator (sodium citrate + sodium hydrosulfide) is added first for activation pulp conditioning, and then the collector amyl xanthate is added. After five full-open-circuit sulfur-oxygen mixed flotation processes, the copper-cobalt oxide concentrate is obtained.

[0030] Example 2

[0031] The process flow of this embodiment is the same as that of Example 1. The main difference is that the total dosage of the high-efficiency combined regulator is 1450 g / t of the original ore dry weight, which includes 350 g / t of the original ore dry weight of sodium citrate and 1100 g / t of the original ore dry weight of sodium hydrosulfide.

[0032] Before the second and third stage flotation, a high-efficiency combined regulator (100 g / t of sodium citrate based on the dry weight of the original ore + 400 g / t of sodium hydrosulfide based on the dry weight of the original ore) is added first and stirred for pulp conditioning for 2 minutes. Then, 400 g / t of amyl xanthate (PAX) as a collector is added and stirred for 2 minutes. Finally, flotation is started. The flotation time for both the second and third stages is 5 minutes. Before the fourth stage flotation, a high-efficiency combined collector (100 g / t of sodium citrate based on the dry weight of the original ore + 200 g / t of sodium hydrosulfide based on the dry weight of the original ore) is added and stirred for pulp conditioning for 2 minutes. Then, 300 g / t of amyl xanthate (PAX) as a collector is added and stirred for 2 minutes. The flotation time is 4 minutes. Before the fifth stage flotation, a high-efficiency combined collector (50 g / t of sodium citrate based on the dry weight of the original ore + 100 g / t of sodium hydrosulfide based on the dry weight of the original ore) is added and stirred for pulp conditioning for 2 minutes. Then, 200 g / t of amyl xanthate (PAX) as a collector is added and stirred for 2 minutes. The flotation time is 3 minutes. The tailings remaining from each stage of flotation enter the next stage of flotation. The concentrates obtained from each stage of flotation are mixed to obtain the final copper oxide cobalt concentrate, and the tailings remaining after the fifth stage of flotation are the final tailings.

[0033] Example 3

[0034] The process flow of this example is the same as that of Example 1. The main difference is that the total dosage of the high-efficiency combined regulator is 1450 g / t of the dry weight of the original ore, which includes 250 g / t of sodium citrate and 1200 g / t of sodium hydrosulfide based on the dry weight of the original ore.

[0035] Before the second and third stage flotation, a high-efficiency combined regulator (100 g / t of sodium citrate based on the dry weight of the original ore + 400 g / t of sodium hydrosulfide based on the dry weight of the original ore) is added first and stirred for pulp conditioning for 2 minutes. Then, 400 g / t of amyl xanthate (PAX) as a collector is added and stirred for 2 minutes. Finally, flotation is started. The flotation time for both the second and third stages is 5 minutes. Before the fourth stage flotation, a high-efficiency combined collector (30 g / t of sodium citrate based on the dry weight of the original ore + 200 g / t of sodium hydrosulfide based on the dry weight of the original ore) is added and stirred for pulp conditioning for 2 minutes. Then, 300 g / t of amyl xanthate (PAX) as a collector is added and stirred for 2 minutes. The flotation time is 4 minutes. Before the fifth stage flotation, a high-efficiency combined collector (20 g / t of sodium citrate based on the dry weight of the original ore + 200 g / t of sodium hydrosulfide based on the dry weight of the original ore) is added and stirred for pulp conditioning for 2 minutes. Then, 200 g / t of amyl xanthate (PAX) as a collector is added and stirred for 2 minutes. The flotation time is 3 minutes. The tailings remaining from each stage of flotation enter the next stage of flotation. The concentrates obtained from each stage of flotation are mixed to obtain the final copper oxide cobalt concentrate, and the tailings remaining after the fifth stage of flotation are the final tailings.

[0036] Comparative Example 1

[0037] A certain copper-cobalt oxide ore contains about 2.30% copper and about 0.20% cobalt in the raw ore. The characteristics of the ore are as follows: ① high oxidation rate, about 95%; ② serious slime, poor separation efficiency between valuable minerals and gangue minerals, and low recovery rates of copper and cobalt metals. The copper metal in the ore is mainly hosted in malachite, chrysocolla, and chalcopyrite, and the cobalt metal is mainly distributed in hydrocobaltite, cobaltite, and cobalt carbonate. The gangue minerals are mainly dolomite, quartz, and chlorite, with serious slime. Under the influence of slime, the separation efficiency of the flotation concentrate using conventional regulators is poor, and the recovery rates of copper and cobalt are low. Using the ore dressing method in Example 1 of the present invention to treat the above ore, the obtained indexes are shown in Table 1.

[0038] Using the same above ore, replace the high-efficiency combined regulator in the method of Example 1 with the conventional regulator sodium hydrosulfide as Comparative Example 1. The total dosage of the conventional regulator is 2050 g / t of the dry weight of the raw ore.

[0039] The process indexes of Example 1 and Comparative Example 1 are shown in Table 1

[0040] Table 1

[0041]

[0042] As can be seen from Table 1, better ore dressing indexes are obtained in this example. The test results show that the recovery rate of copper in the method of Example 1 is increased by 4.66%, the recovery rate of cobalt is increased by 1.64%, the copper grade is increased by 0.55%, and the cobalt grade is increased by 0.09%.

[0043] Comparative Example 2

[0044] A certain copper-cobalt oxide ore contains about 2.00% copper and about 0.10% cobalt in the raw ore. The characteristics of the ore are as follows: ① high oxidation rate, about 96% for copper and cobalt oxidation rate; ② low recovery efficiency of copper and cobalt metals. The copper minerals in the ore are mainly malachite; the iron minerals are mainly limonite; the other metals mainly include cobalt carbonate and a small amount of cobaltite; the non-metallic cobalt minerals mainly include quartz, dolomite, chlorite, etc. The recovery rates of copper and cobalt are low using conventional regulators.

[0045] Using the ore dressing method in Example 2 of the present invention to treat the above ore, the obtained process indexes are shown in Table 2.

[0046] Using the same above ore, replace the high-efficiency combined regulator in the method of Example 2 with the conventional regulator sodium hydrosulfide as Comparative Example 2. The total dosage of the conventional regulator is 2050 g / t of the dry weight of the raw ore.

[0047] The process indexes of Example 2 and Comparative Example 2 are shown in Table 1

[0048] Table 2

[0049]

[0050] As can be seen from Table 2, the method of Example 2 achieved better ore dressing indexes. The test results show that the recovery rate of copper by the method of Example 2 increased by 1.99%, and the recovery rate of cobalt increased by 0.24%.

[0051] For those skilled in the art, various corresponding changes and deformations can be given according to the above technical solutions and concepts, and all such changes and deformations should be included within the protection scope of the claims of the present invention.

Claims

1. An efficient combined regulator for easily sludged copper-cobalt oxide ores, characterized in that: The invention comprises 250-350 parts of sodium citrate and 1100-1200 parts of sodium hydrosulfide by weight.

2. A method for beneficiating easily muddy copper-cobalt oxide ore using the high-efficiency combined regulator according to claim 1, characterized in that: The steps include: S1, crush the raw ore for later use; S2, mixing the crushed ore obtained in step S1 with water and grinding the ore to obtain a floatable product; S3, subjecting the floatable product obtained in step S2 to multi-stage mixed flotation of sulfide ore and oxide ore; in the first stage of flotation, a regulator NaHS, a collector and a frother are added to pre-float out a portion of fine mud; After the first stage of flotation, the tailings remaining after a part of the fine mud is floated out are subjected to subsequent flotation; before each subsequent stage of flotation, the high-efficiency combined regulator and collector described in claim 1 are added in advance, and flotation is performed after stirring and slurrying to obtain concentrates and tailings. The tailings remaining in each stage of flotation enter the next stage of flotation, and the concentrates obtained in each stage of flotation are mixed to obtain the final copper-cobalt oxide concentrate. The tailings remaining after the fifth stage of flotation are the final tailings.

3. The method according to claim 2, characterized in that In step S1, the raw ore is crushed to a particle size of ≤2 mm.

4. The method according to claim 2, characterized in that: In step S2, the ore is ground using a ball mill, the ball mill uses iron ball media and the filling rate of the iron ball media is 32%.

5. The method according to claim 2, characterized in that: In the floatable product obtained in step S2, the portion with a particle size of ≤74 μm accounts for 67-77% of the total mass of the floatable product.

6. The method according to claim 2, characterized in that In step S3, in the first stage of flotation, the pH of the ore pulp is 9-10, and the mass concentration of the ore pulp is 28-34%; the dosage of the adjusting agent NaHS in the first stage of flotation is 500-700 g / t of the dry weight of the original ore, the collector used includes amyl xanthate, the dosage is 500-700 g / t of the dry weight of the original ore, and the frother used includes 2 # Oil, the dosage is 20-40g / t dry weight of the original ore.

7. The method according to claim 6, characterized in that In step S3, in each flotation after the first flotation, the collector used includes amyl xanthate.

8. The method according to claim 7, characterized in that In step S3, the total amount of amyl xanthate used as the collector in all flotation stages is 1800-1900 g / t dry weight of the original ore.

9. The method according to claim 2, characterized in that: In step S3, the total amount of the high-efficiency combined adjusting agent used in all stages of flotation is 250-350 g of sodium citrate and 1100-1200 g of sodium hydrosulfide per ton of dry weight of the original ore.

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